Liquid Cleaning And/Or Cleansing Composition

ABSTRACT

The present invention relates to a liquid, cleaning and/or cleansing composition comprising abrasive cleaning particles.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.61/288,887 filed Dec. 22, 2009; and U.S. Provisional Application No.61/326,286, filed Apr. 21, 2010; and U.S. Provisional Application No.61/326,290, filed Apr. 21, 2010.

TECHNICAL FIELD

The present invention relates to liquid compositions for cleaning and/orcleansing a variety of inanimate and animate surfaces, including hardsurfaces in and around the house, dish surfaces, human and animal skin,car and vehicles surfaces, etc. More specifically, the present inventionrelates to liquid scouring compositions comprising suitable particlesfor cleaning and/or cleansing.

BACKGROUND OF THE INVENTION

Scouring compositions such as particulate compositions or liquid (incl.gel, paste-type) compositions containing abrasive components are wellknown in the art. Such compositions are used for cleaning and/orcleansing a variety of surfaces; especially those surfaces that tend tobecome soiled with difficult to remove stains and soils.

Amongst the currently known scouring compositions, the most popular onesare based on abrasive particles with shapes varying from spherical toirregular. The most common abrasive particles are either inorganic likecarbonate salt, clay, silica, silicate, shale ash, perlite and quartzsand or organic polymeric beads like polypropylene, PVC, melamine, urea,polyacrylate and derivatives, and come in the form of liquid compositionhaving a creamy consistency with the abrasive particles suspendedtherein.

The surface safety profile of such currently known scouring compositionsis inadequate alternatively, poor cleaning performances is shown forcompositions with an adequate surface safety profile. Indeed, due to thepresence of very hard abrasive particles, these compositions can damage,i.e., scratch, the surfaces onto which they have been applied while withless hard material the level of cleaning performance is insufficient.Indeed, the formulator needs to choose between good cleaning/cleansingperformance but featuring strong surface damage or compromising on thecleaning/cleansing performance while featuring an acceptable surfacesafety profile. In addition, such currently known scouring compositionsat least in certain fields of application (e.g., hard surface cleaning)are perceived by consumers as outdated.

It is thus an objective of the present invention to provide a liquidcleaning and/or cleansing composition suitable to clean/cleanse avariety of surfaces, including inanimate and animate surfaces, such hardsurfaces in and around the house, dish surfaces, hard and soft tissuesurface of the oral cavity, such as teeth, gums, tongue and buccalsurfaces, human and animal skin, etc., wherein the composition providesgood cleaning/cleansing performance, whilst providing a good surfacesafety profile.

It has been found that the above objective can be met by the compositionaccording to the present invention.

It is an advantage of the compositions according to the presentinvention that they may be used to clean/cleanse inanimate and animatesurfaces made of a variety of materials like glazed and non-glazedceramic tiles, enamel, stainless steel, Inox®, Formica®, vinyl, no-waxvinyl, linoleum, melamine, glass, plastics, painted surfaces, human andanimal skin, hair, hard and soft tissue surface of the oral cavity, suchas teeth, gums, tongue and buccal surfaces, and the like.

A further advantage of the present invention is that in the compositionsherein, the particles can be formulated at very low levels, whilst stillproviding the above benefits. Indeed, in general for other technologies,high levels of abrasive particles are needed to reach goodcleaning/cleansing performance, thus leading to high formulation andprocess cost, incompatibility with many package e.g.: squeeze or spraybottle, low incident usage ergonomy, difficult rinse and end cleaningprofiles, as well as limitation for aesthetics and a pleasant hand feelof the cleaning/cleansing composition.

SUMMARY OF THE INVENTION

The present invention is directed to a liquid cleaning and/or cleansingcomposition comprising abrasive cleaning particles, wherein saidabrasive cleaning particles have a mean circularity from 0.1 to 0.4 andwherein said abrasive cleaning particles have a HV Vickers hardness from3 to 50 kg/mm².

The present invention further encompasses a process of cleaning and/orcleansing a surface with a liquid, cleaning and/or cleansing compositioncomprising abrasive cleaning particles, wherein said surface iscontacted with said composition, preferably wherein said composition isapplied onto said surface.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is an illustration of tip radius.

FIG. 2 is an illustration how to calculate roughness from the particle.

DETAILED DESCRIPTION OF THE INVENTION The Liquid Cleaning/CleansingComposition

The compositions according to the present invention are designed ascleaners/cleansers for a variety of inanimate and animate surfaces.Preferably, the compositions herein are suitable for cleaning/cleansingsurfaces selected from the group consisting of inanimate surfaces andanimate surfaces.

In a preferred embodiment, the compositions herein are suitable forcleaning/cleansing inanimate surfaces selected from the group consistingof household hard surfaces; dish surfaces; surfaces like leather orsynthetic leather; and automotive vehicles surfaces.

In a highly preferred embodiment, the compositions herein are suitableto clean household hard surfaces.

By “household hard surface”, it is meant herein any kind of surfacetypically found in and around houses like kitchens, bathrooms, e.g.,floors, walls, tiles, windows, cupboards, sinks, showers, showerplastified curtains, wash basins, WCs, fixtures and fittings and thelike made of different materials like ceramic, vinyl, no-wax vinyl,linoleum, melamine, glass, Inox®, Formica®, any plastics, plastifiedwood, metal or any painted or varnished or sealed surface and the like.Household hard surfaces also include household appliances including, butnot limited to refrigerators, freezers, washing machines, automaticdryers, ovens, microwave ovens, dishwashers and so on. Such hardsurfaces may be found both in private households as well as incommercial, institutional and industrial environments.

By “dish surfaces” it is meant herein any kind of surfaces found in dishcleaning, such as dishes, cutlery, cutting boards, pans, and the like.Such dish surfaces may be found both in private households as well as incommercial, institutional and industrial environments.

In an another preferred embodiment, the compositions herein are suitablefor cleaning/cleansing animate surfaces selected from the groupconsisting of human skin; animal skin; human hair; animal hair; and hardand soft tissue surface of the oral cavity, such as teeth, gums, tongueand buccal surfaces.

The compositions according to the present invention are liquidcompositions as opposed to a solid or a gas. Liquid compositions includecompositions having a water-like viscosity as well as thickenedcompositions, such as gels and pastes.

In a preferred embodiment herein, the liquid compositions herein areaqueous compositions. Therefore, they may comprise from 65% to 99.5% byweight of the total composition of water, preferably from 75% to 98% andmore preferably from 80% to 95%.

In an another preferred embodiment herein, the liquid compositionsherein are mostly non-aqueous compositions although they may comprisefrom 0% to 10% by weight of the total composition of water, preferablyfrom 0% to 5%, more preferably from 0% to 1% and most preferably 0% byweight of the total composition of water.

In a preferred embodiment herein, the compositions herein are neutralcompositions, and thus have a pH, as is measured at 25° C., of 6-8, morepreferably 6.5-7.5, even more preferably 7.

In other preferred embodiment compositions have pH preferably above pH 4and alternatively have pH preferably below pH 9.

Accordingly, the compositions herein may comprise suitable bases andacids to adjust the pH.

A suitable base to be used herein is an organic and/or inorganic base.Suitable bases for use herein are the caustic alkalis, such as sodiumhydroxide, potassium hydroxide and/or lithium hydroxide, and/or thealkali metal oxides such, as sodium and/or potassium oxide or mixturesthereof. A preferred base is a caustic alkali, more preferably sodiumhydroxide and/or potassium hydroxide.

Other suitable bases include ammonia, ammonium carbonate, all availablecarbonate salts such as K₂CO₃, Na₂CO₃, Ca₂CO₃, Mg₂CO₃, etc.,alkanolamines (as e.g. monoethanolamine), urea and urea derivatives,polyamine, etc.

Typical levels of such bases, when present, are of from 0.01% to 5.0% byweight of the total composition, preferably from 0.05% to 3.0% and morepreferably from 0.1% to 0.6%.

The compositions herein may comprise an acid to trim its pH to therequired level, despite the presence of an acid, if any, thecompositions herein will maintain their preferred neutral pH asdescribed herein above. A suitable acid for use herein is an organicand/or an inorganic acid. A preferred organic acid for use herein has apKa of less than 6. A suitable organic acid is selected from the groupconsisting of citric acid, lactic acid, glycolic acid, succinic acid,glutaric acid and adipic acid and a mixture thereof. A mixture of saidacids may be commercially available from BASF under the trade nameSokalan® DCS. A suitable inorganic acid is selected from the groupconsisting hydrochloric acid, sulphuric acid, phosphoric acid and amixture thereof.

A typical level of such an acid, when present, is of from 0.01% to 5.0%by weight of the total composition, preferably from 0.04% to 3.0% andmore preferably from 0.05% to 1.5%.

In a preferred embodiment according to the present invention thecompositions herein are thickened compositions. Preferably, the liquidcompositions herein have a viscosity of up to 7500 cps at 20 s⁻¹, morepreferably from 5000 cps to 50 cps, yet more preferably from 2000 cps to50 cps and most preferably from 1500 cps to 300 cps at 20 s⁻¹ and 20° C.when measured with a Rheometer, model AR 1000 (Supplied by TAInstruments) with a 4 cm conic spindle in stainless steel, 2° angle(linear increment from 0.1 to 100 sec⁻¹ in max. 8 minutes).

In another preferred embodiment according to the present invention thecompositions herein have a water-like viscosity. By “water-likeviscosity” it is meant herein a viscosity that is close to that ofwater. Preferably the liquid compositions herein have a viscosity of upto 50 cps at 60 rpm, more preferably from 0 cps to 30 cps, yet morepreferably from 0 cps to 20 cps and most preferably from 0 cps to 10 cpsat 60 rpm and 20° C. when measured with a Brookfield digital viscometermodel DV II, with spindle 2.

Abrasive Cleaning Particles

The liquid cleaning and/or cleansing composition herein compriseabrasive cleaning particles that are selected or synthesized to featureeffective shapes, e.g.: defined by circularity and adequate hardness.

In a preferred embodiment the abrasive cleaning particles are preferablynon-rolling. Additionally, in a preferred embodiment the abrasivecleaning particles are preferably sharp.

The applicant has found that non-rolling and sharp abrasive cleaningparticles provide good soil removal and low surface damage. Indeed theapplicant has found that very specific particle shapes e.g.: defined bycircularity to promote effective sliding of the abrasive particles vs.typical abrasive particles, where rolling movement is rather promotedand is less effective as displacing soil from the surface. Thecircularity to meet the criteria, to promote effective sliding of theparticles is at range from 0.1 to 0.4.

The shape of the abrasive cleaning particle can be defined in variousways. The present invention defines the cleaning particle shape in aform of particle, which reflects the geometrical proportions of aparticle and more pragmatically of the particle population. Very recentanalytical techniques allow an accurate simultaneous measurement ofparticle shapes from a large number of particles, typically greater than10000 particles (preferably above 100 000). This enables accurate tuningand/or selection of average particle population shape withdiscriminative performance. These measurement analyses of particle shapeare conducted using on Occhio Nano 500 Particle CharacterisationInstrument with its accompanying software Callistro version 25 (Occhios.a. Liege, Belgium). This instrument is used to prepare, disperse,image and analyse the particle samples, as per manufacturer'sinstructions, and the following instrument setting selections: WhiteRequested=180, vacuum time=5000 ms, sedimentation time=5000 ms,automatic threshold, number of particles counted/analyses=8000 to500000, minimum number of replicates/sample=3, lens setting 1×/1.5×.

The abrasive cleaning particles of the present invention are defined byquantitative description of a shape. In quantitative description, shapedescriptor is understood as numbers that can be calculated from particleimages or physical particle properties via mathematical or numericaloperations. While particle shape can be defined in 3-dimension withdedicated analytical technique, the applicant has found, that thecharacterization of the particles shape in 2-dimension is most relevantand correlates with the abrasive performance of the cleaning particles.During the particle shape analysis protocol, the particles areorientated toward the surface—via gravity deposition—similarly to theexpected particle orientation during the cleaning process. Hence, theobject of the present invention regards the characterization of 2-Dshape of a particle/particle population as defined by the projection ofits shape on the surface on which the particle/particle population isdeposited.

In a preferred embodiment, the abrasive cleaning particles have a meanECD from 10 μm to 1000 μm, preferably from 50 μm to 500 μm, morepreferably from 100 μm to 350 μm and most preferably from 150 to 250 μm.

Indeed, the Applicant has found that the abrasive particle size can becritical to achieve efficient cleaning performance whereas excessivelyabrasive population with small particle sizes e.g.: typically below 10micrometers feature polishing action vs. cleaning despite featuring ahigh number of particles per particle load in cleaner inherent to thesmall particle size. On the other hand, abrasive population withexcessively high particle size, e.g.: above 1000 micrometers, do notdeliver optimal cleaning efficiency, because the number of particles perparticle load in cleaner, decreases significantly inherently to thelarge particle size. Additionally, excessively small particle size arenot desirable in cleaner/for cleaning task since in practice, small andnumerous particles are often hard to remove from the various surfacetopologies which requires excessive effort to remove from the userunless leaving the surface with visible particles residue. On the otherhand, excessively large particle are too easily detected visually orprovide bad tactile experience while handling or using the cleaner.Therefore, the applicant defines herein an optimal particle size rangethat delivers both optimal cleaning performance and usage experience.

The abrasive particles have a size defined by their area-equivalentdiameter (ISO 9276-6:2008(E) section 7) also called Equivalent CircleDiameter ECD (ASTM F1877-05 Section 11.3.2). Mean ECD of particlepopulation is calculated as the average of respective ECD of eachparticles of a particle population of at least 10 000 particles,preferably above 50 000 particles, more preferably above 100 000particles after excluding from the measurement and calculation the dataof particles having area-equivalent diameter (ECD) of below 10micrometers. Mean data are extracted from volume-based vs. number-basedmeasurements.

In one preferred example, the size of the abrasive cleaning particlesused in the present invention is altered during usage especiallyundergoing significant size reduction. Hence the particle remain visibleor tactile detectable in liquid composition and in the beginning of theusage process to provide effective cleaning. As the cleaning processprogresses, the abrasive particles disperse or break into smallerparticles and become invisible to an eye or tactile undetectable.

In the present invention shape descriptors are calculations ofgeometrical descriptors/shape factors. Geometrical shape factors areratios between two different geometrical properties, such properties areusually a measure of proportions of the image of the whole particle or ameasure of the proportions of an ideal geometrical body enveloping theparticle or forms an envelope around the particle. These results aremacroshape descriptors similar to aspect ratio, however the Applicanthas discovered that mesoshape descriptors—a specific sub-class ofmacroshape descriptor—are particularly critical to the cleaningeffectiveness and surface safety performances of the abrasive cleaningparticles, while more typical shape parameters such as aspect ratio hasproved insufficient. These mesoshape descriptors describe how differenta particle is compared to an an ideal geometrical shape, especially howdifferent compared to a sphere, and incidentally help define its abilityfor non-rolling, e.g.: sliding, effective cleaning movement pattern. Theabrasive cleaning particles of the present invention are different fromtypical spherical or spherical-resembling e.g.: granular, abrasivesforms.

The abrasive cleaning particles of the present invention arenon-spherical.

The non-spherical particles herein preferably have sharp edges and eachparticle has at least one edge or surface having concave curvature. Morepreferably, the non-spherical particles herein have a multitude of sharpedges and each particle has at least one edge or surface having concavecurvature. The sharp edges of the non-spherical particles are defined byedge having a tip radius below 20 μm, preferably below 8 μm, mostpreferably below 5 μm. The tip radius is defined by the diameter of animaginary circle fitting the curvature of the edge extremity.

FIG. 1 is an illustration of tip radius.

Circularity

Circularity is a quantitative, 2-dimension image analysis shapedescription and is being measured according to ISO 9276-6:2008(E)section 8.2 as implemented via the Occhio Nano 500 ParticleCharacterisation Instrument with its accompanying software Callistroversion 25 (Occhio s.a. Liege, Belgium). Circularity is a preferredMesoshape descriptor and is widely available in shape analysisinstrument such as in Occhio Nano 500 or in Malvern Morphologi G3.Circularity is sometimes described in literature as being the differencebetween a particle's shape and a perfect sphere. Circularity valuesrange from 0 to 1, where a circularity of 1 describes a perfectlyspherical particles or disc particle as measured in a two dimensionalimage.

$C = \sqrt{\frac{4\pi \; A}{P^{2}}}$

Where A is projection area, which is 2D descriptor and P is the lengthof the perimeter of the particle.

The applicant has found out that the abrasive cleaning particles havinga mean circularity from 0.1 to 0.40, preferably from 0.15 to 0.35 andmore preferably from 0.2 to 0.35 are providing improved cleaningperformance and surface safety. Mean data are extracted fromvolume-based vs. number-based measurements.

Thus, in a preferred embodiment of the present invention the abrasiveparticles herein have a mean circularity from 0.1 to 0.4, preferablyfrom 0.15 to 0.35, and more preferably from 0.2 to 0.35.

Solidity

Solidity is a quantitative, 2-dimensional image analysis shapedescription, and is being measured according to ISO 9276-6:2008(E)section 8.2 as implemented via the Occhio Nano 500 ParticleCharacterisation Instrument with its accompanying software Callistroversion 25 (Occhio s.a. Liege, Belgium). The non-spherical particleherein has preferably at least one edge or surface having a concavecurvature. Solidity is a mesoshape parameter, which describes theoverall concavity of a particle/particle population. Solidity valuesrange from 0 to 1, where a solidity number of 1 describes a non-concaveparticle, as measured in literature as being:

Solidity=A/Ac

Where A is the area of the particle and Ac is the area of the convexhull (envelope) of bounding the particle.

The applicant has found out that the abrasive cleaning particles havinga mean solidity from 0.4 to 0.75, preferably solidity from 0.5 to 0.7and more preferably from 0.55 to 0.65 are providing improved cleaningperformance and surface safety. Mean data are extracted fromvolume-based vs. number-based measurements.

Thus, in a preferred embodiment of the present invention the abrasiveparticles herein have a mean solidity from 0.4 to 0.75, preferablysolidity from 0.5 to 0.7, and more preferably from 0.55 to 0.65.

Solidity is sometime also named Convexity in literature or in someapparatus software using the solidity formula in place of its definitiondescribed in ISO 9276-6 (convexity=Pc/P where P is the length of theperimeter of the particle and Pc is length of the perimeter of theconvex hull—envelope—bounding the particle). Despite solidity andconvexity being similar mesoshape descriptor in concept, the applicantrefers herein to the solidity measure expressed above by the Occhio Nano500, as indicated above.

Roughness

Roughness is a quantative, 2-dimensional image analysis shapedescription, and is being measured according to ISO 9276-6:2008(E)section 8.2 as implemented via the Occhio Nano 500 ParticleCharacterisation Instrument with its accompanying software Callistroversion 25 (Occhio s.a. Liege, Belgium). Roughness defines 2Dmeasurements, the equivalent useful surface area outside of the coresurface area of the particle, and can range in value from 0 to 1, wherea Roughness value of 0 describes a particle with no useful massavailable at the periphery of the particles core. Roughness is alsosometimes called satellity, and is quantitative description, and isavailable mesoshape descriptor e.g.: in the Occhio Nano 500 instrument.

Roughness is useful in abrasive particles since the non-sphericalparticle herein has preferably a significant mass of material, availableat the periphery of its core, as useful abrasives. This peripheral massis useful for cleaning performance and also for preventing the particlefrom rolling.

Roughness is defining in 2D measurements the equivalent useful surfacearea outside of the core surface area of the particles ranging 0-1whereas a Roughness of 0 describes a particle with no useful massavailable at the periphery of the core particle mass. Roughness iscalculated as follows:

Rgγ=(A−A(Oγ)/A

Where A is the area of the particle and A(Oγ) is the surface area ofwhat is considered the “core of the particle”. A−A(Oγ) represent the“useful area at the periphery of the particle and the Roughnessrepresents the fraction of that useful area vs. the total particle area.Oγ is called the tunable tolerance factor and is typically set at 0.8,therefore the Roughness definition is Rgγ=(A−A(0.8)/A. In order tocalculate the A(0.8), the maximum amount of discs are inscribed withinthe particle contour at each point of the particle's edge. The size,e.g.: area of the discs inscribed is defined by the Discs' diameterswhereas the diameter value ranges between 0.8× Dmax and Dmax (where Dmaxis the diameter value of the biggest disc inscribed in the particle).The core area of the particle A(0.8) is defined by the areacorresponding to the projection of all the inscribed discs.

FIG. 2 is an illustration how to calculate Roughness from the particle.

The applicant has found that the abrasive cleaning particles having amean roughness from 0.1 to 0.3, preferably from 0.15 to 0.28 and morepreferably from 0.18 to 0.25 are providing improved cleaning performanceand surface safety. Mean data are extracted from volume-based vs.number-based measurements.

Thus, in a preferred embodiment of the present invention the abrasiveparticles herein have a mean roughness from 0.1 to 0.3, preferably from0.15 to 0.28, and more preferably from 0.18 to 0.25.

In highly preferred embodiment the abrasive cleaning particles have amean circularity from 0.1 to 0.4 (preferably from 0.15 to 0.35 and morepreferably from 0.2 to 0.35) and a mean roughness from 0.1 to 0.3(preferably from 0.15 to 0.28 and more preferably from 0.18 to 0.25)and/or a mean solidity from 0.4 to 0.75 (preferably solidity from 0.5 to0.7, and more preferably from 0.55 to 0.65).

By the term “mean circularity”, “mean solidity” or “mean roughness”, theapplicant considers the average of the circularity or solidity orroughness values of each particle taken from a population of at least 10000 particles, preferably above 50 000 particles, more preferably above100 000 particles, after excluding from the measurement and calculation,the circularity or solidity or roughness data of particles havingarea-equivalent diameter (ECD) of below 10 micrometers. Mean data areextracted from volume-based vs. number-based measurements.

The abrasive particles are made of following the material or mixture ofabrasive material typically known in the art such without beingexhaustive e.g.: organic or inorganic salt abrasives such ascarbonate-derived salts, phosphate-derived salts, pyrophosphate-derivedsalts, silica or alumina derived salts, hydroxyapatite, diatomaceous,fuller earth, talk, etc., polymeric abrasives containing polyethylene,polypropylene, PVC, polycarbonate, melamine, urea, polyurethane,polyacrylate, polystyrene, phenolic, polyesters, polyamide, or naturalabrasives derived from cellulose, lingo-cellulose or shell such as nutshell, apple seeds, olive stones, apricot seed, kernel, wood, bamboo andplants.

Preferably the abrasive particles are made from the polymeric materialselected from the group consisting of polyethylene, polypropylene, PVC,polycarbonate, melamine, urea, polyurethane, polyacrylate, polystyrene,phenolic, polyesters, polyamide and mixtures thereof and naturalabrasives derived from cellulose, lingo-cellulose or shell such as nutshell, apple seeds, olive stones, apricot seed, kernel, wood, bamboo andplants and mixtures thereof. More preferably the abrasive particles aremade from the polymeric material selected from the group consisting ofpolyethylene, polypropylene, PVC, polycarbonate, melamine, urea,polyurethane, polyacrylate, polystyrene, phenolic, polyesters, polyamideand mixtures thereof. Even more preferably the abrasive particles aremade from the polymeric material selected from the group consisting ofpolyurethane, polyester, polyacrylate, polystyrene and mixtures thereof.Most preferably the abrasive particles are made from the rigidpolyurethane made from the diisocyanate (e.g. Lupranate M200R orLupranate M20S) and diol (Lupranol 3423).

Typical shearing or graining methods to reduce the above material inabrasive powder featuring useful shape defined by the targetedcircularity range, so other preparation e.g.: grain shaping methodsdescribed in the art may be employed such as agglomerating, printing,carving, etc. Previous shaping processes are sometimes facilitated bymixing previous abrasive materials as fillers within a thermoplastic orsolidifying matrix. Such processes e.g.: including selection of matrixand respective load of filler are well known in art. A specificallypreferred process to achieve particles matching effective circularityrange consists at foaming the abrasive raw material per se or abrasivematerial dispersed within a matrix and reducing the achieved foam intoabrasive particles with improved efficiency. Foaming processes and foamstructure are typically achieved via gas expansion process, e.g.: eitherby injecting gas or solvent within the abrasive precursor and allowingexpansion by pressure drop and/or increasing of temperature e.g.:extrusion foaming process or more conveniently with in-situ generatedgas followed by hardening of the abrasive precursor e.g.: polyurethanefoaming process. Alternatively, foam structures can also be achieved viaemulsion process, followed by hardening and drying step.

In a highly preferred embodiment herein, in order to achieve thegeometrical shape descriptors of the abrasive cleaning particles (i.e.circularity, roughness and/or solidity) the abrasive cleaning particlesare obtained from foamed polymeric material, which is reduced into theabrasive particles preferably by grinding or milling as described hereinlater on.

The applicant has found that good cleaning efficiency will be achievedwith the abrasive particles, which have been made from a foam havingdensity above 100 kg/m³, and even up to 500 kg/m³. However, theapplicant has surprisingly found that significantly better cleaningeffect can be achieved with the foam density being below 100 kg/m³, morepreferably from 5 kg/m³ to 100 kg/m³ and most preferably from 25 kg/m³to 50 kg/m³.

Similarly, the applicant has found that good cleaning efficiency can beachieved with abrasive particles which have been made from the foamsfeaturing close-cell structures, however, the applicant has surprisinglyfound that significantly better cleaning effect can be achieved withfoam with open-cell structure.

Similarly, the applicant has found that good cleaning efficiency can beachieved the abrasive particles which have been made from the foamsfeaturing cell size ranging from 20 micrometers to 2000 micrometers.However the applicant has surprisingly found that significantly bettercleaning effect can be achieved with the foam featuring cell sizebetween 100-1000 micrometers, more preferably from 200 to 500micrometers and most preferably from 300 to 450 micrometers. Foam cellsize can be measured for instance using protocol described in ASTMD3576.

In a preferred embodiment, in order to favor the reduction of the foaminto a particle, the foam has preferably sufficient brittleness, e.g.;upon stress, the foam has little tendency to deform but rather breakinto particles.

Efficient particles are then produced by accurately grinding the foamstructure to target size and shape as described herein. Hence, forinstance, when large particle size is desired, foam with large cell sizeis desirable and vice-et-versa. Additionally, in order to preserve anoptimal particle shape while reducing the foam structure into aparticle, it is recommended to not target particle size excessivelybelow the dimension of the cell size of the foam. Typically, targetparticle size is not below about half of the foam cell size.

In order to favor the reduction of the foam into particles, the foam haspreferably sufficient brittleness, e.g.: upon stress, the foam haslittle tendency to deform and is liable to fracture. The foam used forthe present invention has preferably a no-detectable phase transition(e.g.; glass transition or melting temperature) or a phase transitiontemperature significantly higher that the usage temperature. Preferablythe phase transition temperature is at least 20° C. preferably 40 degree° C. above usage temperature.

One suitable way of reducing the foam into the abrasive cleaningparticles herein is to grind or mill the foam. Other suitable meansinclude the use of eroding tools such as a high speed eroding wheel withdust collector wherein the surface of the wheel is engraved with apattern or is coated with abrasive sandpaper or the like to promote thefoam to form the abrasive cleaning particles herein.

Alternatively and in a highly preferred embodiment herein, the foam maybe reduced to particles in several stages. First the bulk foam can bebroken into pieces of a few cm dimensions by manually chopping orcutting, or using a mechanical tool such as a lumpbreaker, for examplethe Model 2036 from S Howes, Inc. of Silver Creek, N.Y.

Preferably the abrasive cleaning particles obtained via grinding ormilling operation are single particles, which do not have cellstructure.

Incidentally, it has surprisingly been found that the abrasive cleaningparticles of the present invention show a good cleaning performance evenat relatively low levels, such as preferably from 0.1% to 20%,preferably from 0.3% to 10%, more preferably from 0.5% to 5%, even morepreferably from 1.0% to 3.0%, by weight of the total composition of saidabrasive cleaning particles.

In a preferred embodiment the abrasive particles are obtained from afoam by reducing (preferably by grinding or milling) the foam intoabrasive particles. More preferably the abrasive particles are obtainedfrom foamed polymeric material, wherein polymeric material is selectedfrom the group consisting of polyethylene, polypropylene, PVC,polycarbonate, melamine, urea, polyurethane, polyacrylate, polystyrene,phenolic, polyesters, polyamide and mixtures thereof. Even morepreferably the abrasive particles are obtained from foamed polymericmaterial selected from the group consisting of polyurethane, polyester,polyacrylate, polystyrene and mixtures thereof. Most preferably theabrasive particles are obtained from rigid polyurethane foam made fromthe diisocyanate (e.g. Lupranate M200R or Lupranate M20S) and diol(Lupranol 3423).

The particles used in the present invention can be white, transparent orcolored by use of suitable dyes and/or pigments. Additionally suitablecolor stabilizing agents can be used to stabilize desired color.

Hardness of the Abrasive Particles:

Preferred abrasive cleaning particles suitable for used herein are hardenough to provide good cleaning/cleansing performance, whilst providinga good surface safety profile.

The hardness of the abrasive particles reduced from the foam can bemodified by changing the raw material used to prepare the foam. Forexample modification of the hardness of the polyurethane foam ispossible via several ways. For example, without being exhaustive, theselection of the diisocyanate and especially the selection of theisocyanate with high functionality e.g.: >2, preferably >2.5, mostpreferably above 2.7, increases the polyurethane hardness. Similarly,the use of low molecular weight polyols e.g.: <4000Mw, preferably<2000Mw and most preferably below 1000Mw also increase the polyurethanehardness. More importantly is the balance diisocyanate/polyols in thereaction mixture, although excess of diisocyanate also increase the foamhardness. Another possibility to increase hardness is to introduce asmall molecular weight crosslinker. Alternatively selection of catalyst,will promote the formation of urea bond, is additional way to increasethe foam hardness.

Preferred abrasive cleaning particles in the present invention havehardness from 3 to 50 kg/mm², preferably from 4 to 25 kg/mm² and mostpreferably from 5 to 15 kg/mm² on the HV Vickers hardness.

Vickers Hardness Test Method:

Vickers hardness HV is measured at 23° C. according to standard methodsISO 14577-1, ISO 14577-2, ISO 14577-3. The Vickers hardness is measuredfrom a solid block of the raw material at least 2 mm in thickness. TheVickers hardness micro indentation measurement is carried out by usingthe Micro-Hardness Tester (MHT), manufactured by CSM Instruments SA,Peseux, Switzerland.

As per the ISO 14577 instructions, the test surface should be flat andsmooth, having a roughness (Ra) value less than 5% of the maximumindenter penetration depth. For a 200 μm maximum depth this equates to aRa value less than 10 μm. As per ISO 14577, such a surface may beprepared by any suitable means, which may include cutting the block oftest material with a new sharp microtome or scalpel blade, grinding,polishing or by casting melted material onto a flat, smooth casting formand allowing it to thoroughly solidify prior testing.

Suitable general settings for the Micro-Hardness Tester (MHT) are asfollows:

Control mode: Displacement, Continuous

Maximum displacement: 200 μm

Approach speed: 20 nm/s

Zero point determination: at contact

Hold period to measure thermal drift at contact: 60 s

Force application time: 30 s

Frequency of data logging: at least every second

Hold time at maximum force: 30 s

Force removal time: 30 s

Shape/Material of intender tip: Vickers Pyramid Shape/Diamond Tip

Alternatively, the abrasive cleaning particles in the present inventionhardness may also expressed accordingly to the MOHS hardness scale.Preferably, the MOHS hardness is comprised between 0.5 and 3.5 and mostpreferably between 1 and 3. The MOHS hardness scale is aninternationally recognized scale for measuring the hardness of acompound versus a compound of known hardness, see Encyclopedia ofChemical Technology, Kirk-Othmer, 4 th Edition Vol 1, page 18 or Lide,D. R (ed) CRC Handbook of Chemistry and Physics, 73 rd edition, BocaRaton, Fla.: The Rubber Company, 1992-1993. Many MOHS Test kits arecommercially available containing material with known MOHS hardness. Formeasurement and selection of abrasive material with selected MOHShardness, it is recommended to execute the MOHS hardness measurementwith un-shaped particles e.g.: with spherical or granular forms of theabrasive material since MOHS measurement of shape particles will provideerroneous results.

The applicant has found that by choosing the abrasive cleaning particlesaccording to 2 dimensional shape parameters as described herein,abrasive cleaning particles having a mean circularity from 0.1 to 0.4and Vickers hardness from 3 kg/mm² to 50 kg/mm² and preferably a meansolidity from 0.4 to 0.75 and/or a mean roughness from 0.1 to 0.3 willprovide good cleaning effectiveness and surface safety.

Optional Ingredients

The compositions according to the present invention may comprise avariety of optional ingredients depending on the technical benefit aimedfor and the surface treated.

Suitable optional ingredients for use herein include chelating agents,surfactants, radical scavengers, perfumes, surface-modifying polymers,solvents, builders, buffers, bactericides, hydrotropes, colorants,stabilizers, bleaches, bleach activators, suds controlling agents likefatty acids, enzymes, soil suspenders, brighteners, anti dusting agents,dispersants, pigments, and dyes.

Suspending Aid

The abrasive cleaning particles present in the composition herein aresolid particles in a liquid composition. Said abrasive cleaningparticles may be suspended in the liquid composition. However, it iswell within the scope of the present invention that such abrasivecleaning particles are not-stably suspended within the composition andeither settle or float on top of the composition. In this case, a usermay have to temporally suspend the abrasive cleaning particles byagitating (e.g., shaking or stirring) the composition prior to use.

However, it is preferred herein that the abrasive cleaning particles arestably suspended in the liquid compositions herein. Thus thecompositions herein comprise a suspending aid.

The suspending aid herein may either be a compound specifically chosento provide a suspension of the abrasive cleaning particles in the liquidcompositions of the present invention, such as a structurant, or acompound that also provides another function, such as a thickener or asurfactant (as described herein elsewhere).

Any suitable organic and inorganic suspending aids typically used asgelling, thickening or suspending agents in cleaning/cleansingcompositions and other detergent or cosmetic compositions may be usedherein. Indeed, suitable organic suspending aids include polysaccharidepolymers. In addition or as an alternative, polycarboxylate polymerthickeners may be used herein. Also, in addition or as an alternative ofthe above, layered silicate platelets e.g.: Hectorite, bentonite ormontmorillonites can also be used. Suitable commercially availablelayered silicates are Laponite RD® or Optigel CL® available fromRockwood Additives.

Suitable polycarboxylate polymer thickeners include (preferably lightly)crosslinked polyacrylate. A particularly suitable polycarboxylatepolymer thickener is Carbopol commercially available from Lubrizol underthe trade name Carbopol 674®.

Suitable polysaccharide polymers for use herein include substitutedcellulose materials like carboxymethylcellulose, ethyl cellulose,hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxymethylcellulose, succinoglycan and naturally occurring polysaccharide polymerslike Xanthan gum, gellan gum, guar gum, locust bean gum, tragacanth gum,succinoglucan gum, or derivatives thereof, or mixtures thereof. Xanthangum is commercially available from Kelco under the tradename Kelzan T.

Preferably the suspending aid herein is Xanthan gum. In an alternativeembodiment, the suspending aid herein is a polycarboxylate polymerthickeners preferably a (preferably lightly) crosslinked polyacrylate.In a highly preferred embodiment herein, the liquid compositionscomprise a combination of a polysaccharide polymer or a mixture thereof,preferably Xanthan gum, with a polycarboxylate polymer or a mixturethereof, preferably a crosslinked polyacrylate.

As a preferred example, Xanthan gum is preferably present at levelsbetween 0.1% to 5% by weight of the total composition, more preferablyfrom 0.5% to 2%, even more preferably from 0.8% to 1.2%.

Organic Solvent

As an optional but highly preferred ingredient the composition hereincomprises an organic solvents or mixtures thereof.

The compositions herein comprise from 0% to 30% by weight of the totalcomposition of an organic solvent or a mixture thereof, more preferably1.0% to 20% and most preferably, 2% to 15%.

Suitable solvents can be selected from the group consisting of:aliphatic alcohols, ethers and diethers having from 4 to 14 carbonatoms, preferably from 6 to 12 carbon atoms, and more preferably from 8to 10 carbon atoms; glycols or alkoxylated glycols; glycol ethers;alkoxylated aromatic alcohols; aromatic alcohols; terpenes; and mixturesthereof. Aliphatic alcohols and glycol ether solvents are mostpreferred.

Aliphatic alcohols, of the formula R—OH wherein R is a linear orbranched, saturated or unsaturated alkyl group of from 1 to 20 carbonatoms, preferably from 2 to 15 and more preferably from 5 to 12, aresuitable solvents. Suitable aliphatic alcohols are methanol, ethanol,propanol, isopropanol or mixtures thereof. Among aliphatic alcohols,ethanol and isopropanol are most preferred because of their high vapourpressure and tendency to leave no residue.

Suitable glycols to be used herein are according to the formulaHO—CR₁R₂—OH wherein R₁ and R2 are independently H or a C₂-C₁₀ saturatedor unsaturated aliphatic hydrocarbon chain and/or cyclic. Suitableglycols to be used herein are dodecaneglycol and/or propanediol.

In one preferred embodiment, at least one glycol ether solvent isincorporated in the compositions of the present invention. Particularlypreferred glycol ethers have a terminal C₃-C₆ hydrocarbon attached tofrom one to three ethylene glycol or propylene glycol moieties toprovide the appropriate degree of hydrophobicity and, preferably,surface activity. Examples of commercially available solvents based onethylene glycol chemistry include mono-ethylene glycol n-hexyl ether(Hexyl Cellosolve®) available from Dow Chemical. Examples ofcommercially available solvents based on propylene glycol chemistryinclude the di-, and tri-propylene glycol derivatives of propyl andbutyl alcohol, which are available from Arco under the trade namesArcosolv® and Dowanol®.

In the context of the present invention, preferred solvents are selectedfrom the group consisting of mono-propylene glycol mono-propyl ether,di-propylene glycol mono-propyl ether, mono-propylene glycol mono-butylether, di-propylene glycol mono-propyl ether, di-propylene glycolmono-butyl ether; tri-propylene glycol mono-butyl ether; ethylene glycolmono-butyl ether; di-ethylene glycol mono-butyl ether, ethylene glycolmono-hexyl ether and di-ethylene glycol mono-hexyl ether, and mixturesthereof. “Butyl” includes normal butyl, isobutyl and tertiary butylgroups. Mono-propylene glycol and mono-propylene glycol mono-butyl etherare the most preferred cleaning solvent and are available under thetradenames Dowanol DPnP® and Dowanol DPnB®. Di-propylene glycolmono-t-butyl ether is commercially available from Arco Chemical underthe tradename Arcosolv PTB®.

In a particularly preferred embodiment, the cleaning solvent is purifiedso as to minimize impurities. Such impurities include aldehydes, dimers,trimers, oligomers and other by-products. These have been found todeleteriously affect product odor, perfume solubility and end result.The inventors have also found that common commercial solvents, whichcontain low levels of aldehydes, can cause irreversible and irreparableyellowing of certain surfaces. By purifying the cleaning solvents so asto minimize or eliminate such impurities, surface damage is attenuatedor eliminated.

Though not preferred, terpenes can be used in the present invention.Suitable terpenes to be used herein monocyclic terpenes, dicyclicterpenes and/or acyclic terpenes. Suitable terpenes are: D-limonene;pinene; pine oil; terpinene; terpene derivatives as menthol, terpineol,geraniol, thymol; and the citronella or citronellol types ofingredients.

Suitable alkoxylated aromatic alcohols to be used herein are accordingto the formula R-(A)_(n)-OH wherein R is an alkyl substituted ornon-alkyl substituted aryl group of from 1 to 20 carbon atoms,preferably from 2 to 15 and more preferably from 2 to 10, wherein A isan alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is aninteger of from 1 to 5, preferably 1 to 2. Suitable alkoxylated aromaticalcohols are benzoxyethanol and/or benzoxypropanol.

Suitable aromatic alcohols to be used herein are according to theformula R—OH wherein R is an alkyl substituted or non-alkyl substitutedaryl group of from 1 to 20 carbon atoms, preferably from 1 to 15 andmore preferably from 1 to 10. For example a suitable aromatic alcohol tobe used herein is benzyl alcohol.

Surfactants

The compositions herein may comprise a nonionic, anionic, zwitterionic,cationic and amphoteric surfactant or mixtures thereof. Suitablesurfactants are those selected from the group consisting of nonionic,anionic, zwitterionic, cationic and amphoteric surfactants, havinghydrophobic chains containing from 8 to 18 carbon atoms. Examples ofsuitable surfactants are described in McCutcheon's Vol. 1: Emulsifiersand Detergents, North American Ed., McCutcheon Division, MC PublishingCo., 2002.

Preferably, the composition herein comprises from 0.01% to 20% by weightof the total composition of a surfactant or a mixture thereof, morepreferably from 0.5% to 10%, and most preferably from 1% to 5%.

Non-ionic surfactants are highly preferred for use in the compositionsof the present invention. Non-limiting examples of suitable non-ionicsurfactants include alcohol alkoxylates, alkyl polysaccharides, amineoxides, block copolymers of ethylene oxide and propylene oxide, fluorosurfactants and silicon based surfactants. Preferably, the aqueouscompositions comprise from 0.01% to 20% by weight of the totalcomposition of a non-ionic surfactant or a mixture thereof, morepreferably from 0.5% to 10%, and most preferably from 1% to 5%.

A preferred class of non-ionic surfactants suitable for the presentinvention is alkyl ethoxylates. The alkyl ethoxylates of the presentinvention are either linear or branched, and contain from 8 carbon atomsto 16 carbon atoms in the hydrophobic tail, and from 3 ethylene oxideunits to 25 ethylene oxide units in the hydrophilic head group. Examplesof alkyl ethoxylates include Neodol 91-6®, Neodol 91-8® supplied by theShell Corporation (P.O. Box 2463, 1 Shell Plaza, Houston, Tex.), andAlfonic 810-60® supplied by Condea Corporation, (900 Threadneedle P.O.Box 19029, Houston, Tex.). More preferred alkyl ethoxylates comprisefrom 9 to 12 carbon atoms in the hydrophobic tail, and from 4 to 9 oxideunits in the hydrophilic head group. A most preferred alkyl ethoxylateis C₉₋₁₁ EO₅, available from the Shell Chemical Company under thetradename Neodol 91-5®. Non-ionic ethoxylates can also be derived frombranched alcohols. For example, alcohols can be made from branchedolefin feedstocks such as propylene or butylene. In a preferredembodiment, the branched alcohol is either a 2-propyl-1-heptyl alcoholor 2-butyl-1-octyl alcohol. A desirable branched alcohol ethoxylate is2-propyl-1-heptyl EO7/AO7, manufactured and sold by BASF Corporationunder the tradename Lutensol XP 79/XL 79®.

Another class of non-ionic surfactant suitable for the present inventionis alkyl polysaccharides. Such surfactants are disclosed in U.S. Pat.Nos. 4,565,647, 5,776,872, 5,883,062, and 5,906,973. Among alkylpolysaccharides, alkyl polyglycosides comprising five and/or six carbonsugar rings are preferred, those comprising six carbon sugar rings aremore preferred, and those wherein the six carbon sugar ring is derivedfrom glucose, i.e., alkyl polyglucosides (“APG”), are most preferred.The alkyl substituent in the APG chain length is preferably a saturatedor unsaturated alkyl moiety containing from 8 to 16 carbon atoms, withan average chain length of 10 carbon atoms. C₈-C₁₆ alkyl polyglucosidesare commercially available from several suppliers (e.g., Simusol®surfactants from Seppic Corporation, 75 Quai d'Orsay, 75321 Paris, Cedex7, France, and Glucopon 220®, Glucopon 225®. Glucopon 425®, Plantaren2000 N®, and Plantaren 2000 N UP®, from Cognis Corporation, Postfach 1301 64, D 40551, Dusseldorf, Germany).

Another class of non-ionic surfactant suitable for the present inventionis amine oxide. Amine oxides, particularly those comprising from 10carbon atoms to 16 carbon atoms in the hydrophobic tail, are beneficialbecause of their strong cleaning profile and effectiveness even atlevels below 0.10%. Additionally C₁₀₋₁₆ amine oxides, especially C₁₂-C₁₄amine oxides are excellent solubilizers of perfume. Alternativenon-ionic detergent surfactants for use herein are alkoxylated alcoholsgenerally comprising from 8 to 16 carbon atoms in the hydrophobic alkylchain of the alcohol. Typical alkoxylation groups are propoxy groups orethoxy groups in combination with propoxy groups, yielding alkyl ethoxypropoxylates. Such compounds are commercially available under thetradename Antarox® available from Rhodia (40 Rue de la Haie-Coq F-93306,Aubervilliers Cédex, France) and under the tradename Nonidet® availablefrom Shell Chemical.

The condensation products of ethylene oxide with a hydrophobic baseformed by the condensation of propylene oxide with propylene glycol arealso suitable for use herein. The hydrophobic portion of these compoundswill preferably have a molecular weight of from 1500 to 1800 and willexhibit water insolubility. The addition of polyoxyethylene moieties tothis hydrophobic portion tends to increase the water solubility of themolecule as a whole, and the liquid character of the product is retainedup to the point where the polyoxyethylene content is about 50% of thetotal weight of the condensation product, which corresponds tocondensation with up to 40 moles of ethylene oxide. Examples ofcompounds of this type include certain of the commercially availablePluronic® surfactants, marketed by BASF. Chemically, such surfactantshave the structure (EO)_(x)(PO)_(y)(EO)_(z) or (PO)_(X)(EO)_(y)(PO),wherein x, y, and z are from 1 to 100, preferably 3 to 50. Pluronic®surfactants known to be good wetting surfactants are more preferred. Adescription of the Pluronic® surfactants, and properties thereof,including wetting properties, can be found in the brochure entitled“BASF Performance Chemicals Plutonic® & Tetronic® Surfactants”,available from BASF.

Other suitable though not preferred non-ionic surfactants include thepolyethylene oxide condensates of alkyl phenols, e.g., the condensationproducts of alkyl phenols having an alkyl group containing from 6 to 12carbon atoms in either a straight chain or branched chain configuration,with ethylene oxide, the said ethylene oxide being present in amountsequal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. Thealkyl substituent in such compounds can be derived from oligomerizedpropylene, diisobutylene, or from other sources of iso-octane n-octane,iso-nonane or n-nonane. Other non-ionic surfactants that can be usedinclude those derived from natural sources such as sugars and includeC₈-C₁₆ N-alkyl glucose amide surfactants.

Suitable anionic surfactants for use herein are all those commonly knownby those skilled in the art. Preferably, the anionic surfactants for useherein include alkyl sulphonates, alkyl aryl sulphonates, alkylsulphates, alkyl alkoxylated sulphates, C₆-C₂₀ alkyl alkoxylated linearor branched diphenyl oxide disulphonates, or mixtures thereof.

Suitable alkyl sulphonates for use herein include water-soluble salts oracids of the formula RSO₃M wherein R is a C₆-C₂₀ linear or branched,saturated or unsaturated alkyl group, preferably a C₈-C₁₈ alkyl groupand more preferably a C₁₀-C₁₆ alkyl group, and M is H or a cation, e.g.,an alkali metal cation (e.g., sodium, potassium, lithium), or ammoniumor substituted ammonium (e.g., methyl-, dimethyl-, and trimethylammonium cations and quaternary ammonium cations, such astetramethyl-ammonium and dimethyl piperidinium cations and quaternaryammonium cations derived from alkylamines such as ethylamine,diethylamine, triethylamine, and mixtures thereof, and the like).

Suitable alkyl aryl sulphonates for use herein include water-solublesalts or acids of the formula RSO₃M wherein R is an aryl, preferably abenzyl, substituted by a C₆-C₂₀ linear or branched saturated orunsaturated alkyl group, preferably a C₈-C₁₈ alkyl group and morepreferably a C₁₀-C₁₆ alkyl group, and M is H or a cation, e.g., analkali metal cation (e.g., sodium, potassium, lithium, calcium,magnesium and the like) or ammonium or substituted ammonium (e.g.,methyl-, dimethyl-, and trimethyl ammonium cations and quaternaryammonium cations, such as tetramethyl-ammonium and dimethyl piperidiniumcations and quaternary ammonium cations derived from alkylamines such asethylamine, diethylamine, triethylamine, and mixtures thereof, and thelike).

An example of a C₁₄-C₁₆ alkyl sulphonate is Hostapur® SAS available fromHoechst. An example of commercially available alkyl aryl sulphonate isLauryl aryl sulphonate from Su.Ma. Particularly preferred alkyl arylsulphonates are alkyl benzene sulphonates commercially available undertrade name Nansa® available from Albright&Wilson.

Suitable alkyl sulphate surfactants for use herein are according to theformula R₁SO₄M wherein R₁ represents a hydrocarbon group selected fromthe group consisting of straight or branched alkyl radicals containingfrom 6 to 20 carbon atoms and alkyl phenyl radicals containing from 6 to18 carbon atoms in the alkyl group. M is H or a cation, e.g., an alkalimetal cation (e.g., sodium, potassium, lithium, calcium, magnesium andthe like) or ammonium or substituted ammonium (e.g., methyl-, dimethyl-,and trimethyl ammonium cations and quaternary ammonium cations, such astetramethyl-ammonium and dimethyl piperidinium cations and quaternaryammonium cations derived from alkylamines such as ethylamine,diethylamine, triethylamine, and mixtures thereof, and the like).

Particularly preferred branched alkyl sulphates to be used herein arethose containing from 10 to 14 total carbon atoms like Isalchem 123 AS®.Isalchem 123 AS® commercially available from Enichem is a C₁₂₋₁₃surfactant which is 94% branched. This material can be described asCH₃—(CH₂)_(m)—CH(CH₂OSO₃Na)—(CH₂)_(n)—CH₃ where n+m=8-9. Also preferredalkyl sulphates are the alkyl sulphates where the alkyl chain comprisesa total of 12 carbon atoms, i.e., sodium 2-butyl octyl sulphate. Suchalkyl sulphate is commercially available from Condea under the tradename Isofol® 12S. Particularly suitable liner alkyl sulphonates includeC₁₂-C₁₆ paraffin sulphonate like Hostapur® SAS commercially availablefrom Hoechst.

Suitable alkyl alkoxylated sulphate surfactants for use herein areaccording to the formula RO(A)_(m)SO₃M wherein R is an unsubstitutedC₆-C₂₀ alkyl or hydroxyalkyl group having a C₆-C₂₀ alkyl component,preferably a C₁₂-C₂₀ alkyl or hydroxyalkyl, more preferably C₁₂-C₁₈alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater thanzero, typically between 0.5 and 6, more preferably between 0.5 and 3,and M is H or a cation which can be, for example, a metal cation (e.g.,sodium, potassium, lithium, calcium, magnesium, etc.), ammonium orsubstituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkylpropoxylated sulfates are contemplated herein. Specific examples ofsubstituted ammonium cations include methyl-, dimethyl-,trimethyl-ammonium and quaternary ammonium cations, such astetramethyl-ammonium, dimethyl piperidinium and cations derived fromalkanolamines such as ethylamine, diethylamine, triethylamine, mixturesthereof, and the like. Exemplary surfactants are C₁₂-C₁₈ alkylpolyethoxylate (1.0) sulfate (C₁₂-C₁₈E(1.0)SM), C₁₂-C₁₈ alkylpolyethoxylate (2.25) sulfate (C₁₂-C₁₈E(2.25)SM), C₁₂-C₁₈ alkylpolyethoxylate (3.0) sulfate (C₁₂-C₁₈E(3.0)SM), C₁₂-C₁₈ alkylpolyethoxylate (4.0) sulfate (C₁₂-C₁₈E (4.0)SM), wherein M isconveniently selected from sodium and potassium.

Suitable C₆-C₂₀ alkyl alkoxylated linear or branched diphenyl oxidedisulphonate surfactants for use herein are according to the followingformula:

wherein R is a C₆-C₂₀ linear or branched, saturated or unsaturated alkylgroup, preferably a C₁₂-C₁₈ alkyl group and more preferably a C₁₄-C₁₆alkyl group, and X+ is H or a cation, e.g., an alkali metal cation(e.g., sodium, potassium, lithium, calcium, magnesium and the like).Particularly suitable C₆-C₂₀ alkyl alkoxylated linear or brancheddiphenyl oxide disulphonate surfactants to be used herein are the C₁₂branched di phenyl oxide disulphonic acid and C₁₆ linear diphenyl oxidedisulphonate sodium salt respectively commercially available by DOWunder the trade name Dowfax 2A1® and Dowfax 8390®.

Other anionic surfactants useful herein include salts (including, forexample, sodium, potassium, ammonium, and substituted ammonium saltssuch as mono-, di- and triethanolamine salts) of soap, C₈-C₂₄olefinsulfonates, sulphonated polycarboxylic acids prepared bysulphonation of the pyrolyzed product of alkaline earth metal citrates,e.g., as described in British patent specification No. 1,082,179, C₈-C₂₄alkylpolyglycolethersulfates (containing up to 10 moles of ethyleneoxide); alkyl ester sulfonates such as C₁₄-C₁₆ methyl ester sulfonates;acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenolethylene oxide ether sulfates, alkyl phosphates, isethionates such asthe acyl isethionates, N-acyl taurates, alkyl succinamates andsulfosuccinates, monoesters of sulfosuccinate (especially saturated andunsaturated C₁₂-C₁₈ monoesters) diesters of sulfosuccinate (especiallysaturated and unsaturated C₆-C₁₄ diesters), acyl sarcosinates, sulfatesof alkylpolysaccharides such as the sulfates of alkylpolyglucoside (thenonionic nonsulfated compounds being described below), alkyl polyethoxycarboxylates such as those of the formula RO(CH₂CH₂O)_(k)CH₂COO⁻M⁺wherein R is a C₈-C₂₂ alkyl, k is an integer from 0 to 10, and M is asoluble salt-forming cation. Resin acids and hydrogenated resin acidsare also suitable, such as rosin, hydrogenated rosin, and resin acidsand hydrogenated resin acids present in or derived from tall oil.Further examples are given in “Surface Active Agents and Detergents”(Vol. I and II by Schwartz, Perry and Berch). A variety of suchsurfactants are also generally disclosed in U.S. Pat. No. 3,929,678,issued Dec. 30, 1975 to Laughlin, et al. at Column 23, line 58 throughColumn 29, line 23.

Zwitterionic surfactants represent another class of preferredsurfactants within the context of the present invention.

Zwitterionic surfactants contain both cationic and anionic groups on thesame molecule over a wide pH range. The typical cationic group is aquaternary ammonium group, although other positively charged groups likesulfonium and phosphonium groups can also be used. The typical anionicgroups are carboxylates and sulfonates, preferably sulfonates, althoughother groups like sulfates, phosphates and the like, can be used. Somecommon examples of these detergents are described in the patentliterature: U.S. Pat. Nos. 2,082,275, 2,702,279 and 2,255,082.

A specific example of a zwitterionic surfactant is3-(N-dodecyl-N,N-dimethyl)-2-hydroxypropane-1-sulfonate (Lauryl hydroxylsultaine) available from the McIntyre Company (24601 Governors Highway,University Park, Ill. 60466, USA) under the tradename Mackam LHS®.Another specific zwitterionic surfactant is C₁₂₋₁₄ acylamidopropylene(hydroxypropylene) sulfobetaine that is available from McIntyre underthe tradename Mackam 50-SB®. Other very useful zwitterionic surfactantsinclude hydrocarbyl, e.g., fatty alkylene betaines. A highly preferredzwitterionic surfactant is Empigen BB®, a coco dimethyl betaine producedby Albright & Wilson. Another equally preferred zwitterionic surfactantis Mackam 35HP®, a coco amido propyl betaine produced by McIntyre.

Another class of preferred surfactants comprises the group consisting ofamphoteric surfactants. One suitable amphoteric surfactant is a C₈-C₁₆amido alkylene glycinate surfactant (‘ampho glycinate’). Anothersuitable amphoteric surfactant is a C₈-C₁₆ amido alkylene propionatesurfactant (‘ampho propionate’). Other suitable, amphoteric surfactantsare represented by surfactants such as dodecylbeta-alanine,N-alkyltaurines such as the one prepared by reacting dodecylamine withsodium isethionate according to the teaching of U.S. Pat. No. 2,658,072,N-higher alkylaspartic acids such as those produced according to theteaching of U.S. Pat. No. 2,438,091, and the products sold under thetrade name “Miranol®”, and described in U.S. Pat. No. 2,528,378.

Chelating Agents

One class of optional compounds for use herein includes chelating agentsor mixtures thereof. Chelating agents can be incorporated in thecompositions herein in amounts ranging from 0.0% to 10.0% by weight ofthe total composition, preferably from 0.01% to 5.0%.

Suitable phosphonate chelating agents for use herein may include alkalimetal ethane 1-hydroxy diphosphonates (HEDP), alkylene poly (alkylenephosphonate), as well as amino phosphonate compounds, including aminoaminotri(methylene phosphonic acid) (ATMP), nitrilo trimethylenephosphonates (NTP), ethylene diamine tetra methylene phosphonates, anddiethylene triamine penta methylene phosphonates (DTPMP). Thephosphonate compounds may be present either in their acid form or assalts of different cations on some or all of their acid functionalities.Preferred phosphonate chelating agents to be used herein are diethylenetriamine penta methylene phosphonate (DTPMP) and ethane 1-hydroxydiphosphonate (HEDP). Such phosphonate chelating agents are commerciallyavailable from Monsanto under the trade name DEQUEST®.

Polyfunctionally-substituted aromatic chelating agents may also beuseful in the compositions herein. See U.S. Pat. No. 3,812,044, issuedMay 21, 1974, to Connor et al. Preferred compounds of this type in acidform are dihydroxydisulfobenzenes such as1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelating agent for use herein is ethylenediamine N,N′-disuccinic acid, or alkali metal, or alkaline earth,ammonium or substitutes ammonium salts thereof or mixtures thereof.Ethylenediamine N,N′-disuccinic acids, especially the (S,S) isomer havebeen extensively described in U.S. Pat. No. 4,704,233, Nov. 3, 1987, toHartman and Perkins. Ethylenediamine N,N′-disuccinic acids is, forinstance, commercially available under the tradename ssEDDS® from PalmerResearch Laboratories.

Suitable amino carboxylates for use herein include ethylene diaminetetra acetates, diethylene triamine pentaacetates, diethylene triaminepentaacetate (DTPA),N-hydroxyethylethylenediamine triacetates,nitrilotri-acetates, ethylenediamine tetrapropionates,triethylenetetraaminehexa-acetates, ethanol-diglycines, propylenediamine tetracetic acid (PDTA) and methyl glycine di-acetic acid (MGDA),both in their acid form, or in their alkali metal, ammonium, andsubstituted ammonium salt forms. Particularly suitable aminocarboxylates to be used herein are diethylene triamine penta aceticacid, propylene diamine tetracetic acid (PDTA) which is, for instance,commercially available from BASF under the trade name Triton FS® andmethyl glycine di-acetic acid (MGDA).

Further carboxylate chelating agents for use herein include salicylicacid, aspartic acid, glutamic acid, glycine, malonic acid or mixturesthereof.

Radical Scavenger

The compositions of the present invention may further comprise a radicalscavenger or a mixture thereof.

Suitable radical scavengers for use herein include the well-knownsubstituted mono and dihydroxy benzenes and their analogs, alkyl andaryl carboxylates and mixtures thereof. Preferred such radicalscavengers for use herein include di-tert-butyl hydroxy toluene (BHT),hydroquinone, di-tert-butyl hydroquinone, mono-tert-butyl hydroquinone,tert-butyl-hydroxy anysole, benzoic acid, toluic acid, catechol, t-butylcatechol, benzylamine, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, n-propyl-gallate or mixtures thereof and highly preferred isdi-tert-butyl hydroxy toluene. Such radical scavengers likeN-propyl-gallate may be commercially available from Nipa Laboratoriesunder the trade name Nipanox S1®.

Radical scavengers, when used, may be typically present herein inamounts up to 10% by weight of the total composition and preferably from0.001% to 0.5% by weight. The presence of radical scavengers maycontribute to the chemical stability of the compositions of the presentinvention.

Perfume

Suitable perfume compounds and compositions for use herein are forexample those described in EP-A-0 957 156 under the paragraph entitled“Perfume”, on page 13. The compositions herein may comprise a perfumeingredient, or mixtures thereof, in amounts up to 5.0% by weight of thetotal composition, preferably in amounts of from 0.1% to 1.5%.

Dye

The liquid compositions according to the present invention may becoloured. Accordingly, they may comprise a dye or a mixture thereof.

Delivery Form of the Compositions

The compositions herein may be packaged in a variety of suitablepackaging known to those skilled in the art, such as plastic bottles forpouring liquid compositions, squeeze bottles or bottles equipped with atrigger sprayer for spraying liquid compositions. Alternatively, thepaste-like compositions according to the present invention may by packedin a tube.

In an alternative embodiment herein, the liquid composition herein isimpregnated onto a substrate; preferably the substrate is in the form ofa flexible, thin sheet or a block of material, such as a sponge.

Suitable substrates are woven or non-woven sheets, cellulosic materialbased sheets, sponge or foam with open cell structures e.g.:polyurethane foams, cellulosic foam, melamine foam, etc.

The Process of Cleaning a Surface

The present invention encompasses a process of cleaning and/or cleansinga surface with a liquid composition according to the present invention.Suitable surfaces herein are described herein above under the heading“The liquid cleaning/cleansing composition”.

In a preferred embodiment said surface is contacted with the compositionaccording to the present invention, preferably wherein said compositionis applied onto said surface.

In another preferred embodiment, the process herein comprises the stepsof dispensing (e.g., by spraying, pouring, squeezing) the liquidcomposition according to the present invention from a containercontaining said liquid composition and thereafter cleaning and/orcleansing said surface.

The composition herein may be in its neat form or in its diluted form.

By “in its neat form”, it is to be understood that said liquidcomposition is applied directly onto the surface to be treated withoutundergoing any dilution, i.e., the liquid composition herein is appliedonto the surface as described herein.

By “diluted form”, it is meant herein that said liquid composition isdiluted by the user typically with water. The liquid composition isdiluted prior to use to a typical dilution level of up to 10 times itsweight of water. A usually recommended dilution level is a 10% dilutionof the composition in water.

The composition herein may be applied using an appropriate implement,such as a mop, paper towel, brush (e.g., a toothbrush) or a cloth,soaked in the diluted or neat composition herein. Furthermore, onceapplied onto said surface said composition may be agitated over saidsurface using an appropriate implement. Indeed, said surface may bewiped using a mop, paper towel, brush or a cloth.

The process herein may additionally contain a rinsing step, preferablyafter the application of said composition. By “rinsing”, it is meantherein contacting the surface cleaned/cleansed with the processaccording to the present invention with substantial quantities ofappropriate solvent, typically water, directly after the step ofapplying the liquid composition herein onto said surface. By“substantial quantities”, it is meant herein between 0.01 lt. and 1 lt.of water per m² of surface, more preferably between 0.1 lt. and 1 lt. ofwater per m² of surface.

In a highly preferred embodiment herein, process of cleaning/cleansingis a process of cleaning household hard surfaces with a liquidcomposition according to present invention.

Cleaning Effectiveness

Cleaning Effectiveness test method:

Ceramic tiles (typically glossy, white, ceramic 24 cm×4 cm) are coveredwith 0.3 g of typical greasy soap scum soils mainly based on calciumstearate and artificial body soils commercially available (applied tothe tile via a sprayer). The soiled tiles are then dried in an oven at atemperature of 140° C. for 10-45 minutes, preferably 40 minutes and thenaged between 2 and 12 hours at room temperature (around 20° C.) in acontrolled environment humidity (60-85% RH, preferably 75% RH). Then thesoiled tiles are cleaned using 5 ml of the composition of the presentinvention poured directly on a Spontex® cellulose sponge pre-wetted withwater. The sponge is then mounted on a Wet Abrasion Scrub TesterInstrument (such as made by Sheen Instruments Ltd. Kingston, England)with the particle composition coated side facing the tile. The abrasiontester can be configured to supply pressure (e.g.: 600 g), and move thesponge over the test surface with a set stroke length (e.g.: 30 cm), atset speed (e.g.: 37 strokes per minute). The ability of the compositionto remove greasy soap scum is measured through the number of strokesneeded to perfectly clean the surface, as determined by visualassessment. The lower the number of strokes, the higher the greasy soapscum cleaning ability of the composition.

Cleaning data below are achieved with 1% of Abrasive particles incleaner (3.5% nonionic surfactant C12EO5). Abrasive cleaning particlesused to generate the example cleaning data were made from polyurethanefoam having a Vickers hardness value of 7 kg/mm². The abrasive cleaningparticles are obtained from rigid polyurethane foam by grinding the foaminto abrasive cleaning particles.

Mean Area- equivalent # strokes to Size selection Diameter Mean cleanGreasy (via air sieving) (ECD) Circularity soap scum NO NO particle —— >100 (not clean) 1  125-20 μm  98 μm 0.31 49 2  125-20 μm 107 μm 0.3446 3 250-125 μm 162 μm 0.22 26 4 250-125 μm 212 μm 0.25 32 5 250-125 μm197 μm 0.28 44 6 355-250 μm 238 μm 0.19 21 7 355-250 μm 216 μm 0.23 19 8355-250 μm 280 μm 0.33 33 9  125-20 μm 111 μm 0.41 86 10   125-20 μm 137μm 0.42 104 11  250-125 μm 221 μm 0.47 94 12  355-250 μm 337 μm 0.42 70

Examples 9-12 are comparative examples as the abrasive cleaningparticles are outside the scope of the present invention.

Surface Safety Surface Damage Method:

To measure the surface damage produced by the test particles, mix 0.2 gof the abrasive particles to be tested, with 4 g of an aqueous lotion ofNEODOL C9-11 EO8 surfactant (Shell Chemicals) (3% surfactant by weight).Wet a new cellulose kitchen sponge (such as Spontex®) of dimensions 4cm×8.5 cm (and 4.5 cm thick) with 24 ml of distilled or deionised water,then load by uniformly distributing the surfactant and particle mixtureover one 4 cm×8.5 cm side of the sponge. The sponge is then mounted on aWet Abrasion Scrub Tester Instrument (such as made by Sheen InstrumentsLtd, Kingston, England) with the particle and surfactant coated sidefacing the test surface. The test surface to be used should be a newsheet of uncolored, transparent, virgin Poly(methyl methacrylate) (alsoknown as PMMA, Plexiglass, Perspex, Lucite), having a Vickers HVHardness Value of 25 kg/square mm (+/−2) (as measured using standardtest method ISO 14577). The abrasion tester should be configured tosupply 600 g of pressure and move the sponge over the test surface witha stroke length of 30 cm, at a speed of 37 strokes per minute. The wetabrasion scrub tester is should be allowed to execute 1,000 strokes(i.e.: 1,000 single-direction displacements), then the sponge isre-loaded with an additional 0.2 g of abrasive and 4 g of surfactantlotion. No additional water should be applied when re-loading thesponge. The sponge is to be reloaded in this manner every 1,000 strokes,for ten consecutive loadings (i.e., 10,000 strokes in total per testsurface). Assessment of damage to the test surface is conducted after10,000 strokes have been completed. The sponge should not be replacedduring the test unless it becomes damaged such as torn or ripped. Inwhich case a new sponge should be wetted, loaded and installed as perinstructions for the original sponge, in order to complete the test.

To assess surface damage on the Poly(methyl methacrylate) test surface,visual grading is conducted according to the following 5-level surfacedamage grading scale: 0=I see no scratches; 1=I think I see scratches;2=I definitely see small scratches; 3=I see lots of scratches; 4=I see alot of damage. The Visual Damage Grade is the average of the gradesgiven by 5 independent graders.

Additionally, the surface damage on the Poly(methyl methacrylate) testsurface is also assessed by measuring Roughness of the sponge-abradedsurface, using a Roughness Tester such as the TR 200(PortableTesters.com LLC). Several profile roughness parameters aremeasured, including: average maximum height (Rz); total peak-to-valleyheight (Rt); Maximum peak height (Rp); maximum valley depth (Rv); meanspacing of irregularities (RSm); and skewness (Rsk).

UN- No Shape shaped Surface damage assessment particle particles*particles* Size selection (via air sieving) NA 250-125 μm   250-125 μm  Mean Area-equivalent Diameter (ECD) NA   162 μm   221 μm MeanCircularity NA 0.22 0.47 Mean Solidity NA 0.56 0.82 Mean Roughness NA0.21 0.08 Visual damage grade 0    0.4  2.7  Roughness parameter**: Rz(Average maximum Height of 0.079 μm 0.130 μm 0.271 μm profile) Roughnessparameter**: Rt (total peak-to-valley height) 0.186 μm 0.413 μm 0.906 μmRoughness parameter**: Rp (Maximum Profile Peak 0.061 μm 0.091 μm 0.154μm Height) Roughness parameter**: Rv (Maximum Profile Valley 0.019 μm0.040 μm 0.117 μm Depth) Roughness parameter**: RSm (Mean Spacing ofProfile 7.0833 mm  4.3055 mm  2.2685 mm  Irregularities) Roughnessparameter**: Rsk (Skewness of profil) 2.839  3.065 4.5  *Note Abrasiveparticle made from polyurethane foam with same hardness - Vickershardness value of 7. **Roughness parameter is parameter indicatingsurface damage and is not linked to the Roughness parameter used todefine particle shape.

EXAMPLES

These following compositions were made comprising the listed ingredientsin the listed proportions (weight %). Examples 1-43 herein are met toexemplify the present invention but are not necessarily used to limit orotherwise define the scope of the present invention.

Abrasive particle used in the examples below were ground from rigidpolyurethane foam (controlled foam structure e.g.: foam density, cellsize, strut aspect ratio and % cell size content). Polyurethane foam issynthesized from reaction of a diisocyanate (e.g.: base on polymericmethylene diphenyl diisocyanate) and polyols (e.g.: polyether orpolyester-based polyol). Wherein the diisocyanate is for exampleLupranate M200R from BASF and the polyol is for example Lupranol 3423from BASF. Foam were ground into small particles and sieved using arotary mill and particle selection was done with used of air jet sievinginstrument from Retsch.

Hard surface cleaner Bathroom composition: % Weight 1 2 3 C9-C11 EO8(Neodol 91-8 ®) 3 2.5 3.5 Alkyl Benzene sulfonate 1 C12-14-dimethylAminoxide 1 n-Butoxy Propoxy Propanol 2 2.5 Hydrogene Peroxide 3Hydrophobic ethoxylated polyurethane 1.5 1 0.8 (Acusol 882 ®) LacticAcid 3 3.5 Citric Acid 3 0.5 Polysaccharide (Xanthan Gum, Keltrol 0.250.25 0.25 CG-SFT ® Kelco) Perfume 0.35 0.35 0.35 Abrasive particles madefrom polyurethane 1 1 1 foam having Mean Area-equivalent Diameter (ECD):238 μm; Mean Circularity: 0.19; Mean Solidity: 0.59; Mean Roughness:0.24 Water Balance Balance Balance % Weight 4 5 6 Chloridric acid 2Linear C10 alkyl sulphate 1.3 2 3 n-Butoxy Propoxy Propanol 2 1.75Citric Acid 3 3 PolyvinylPyrrolidone (Luviskol K60 ®) 0.1 0.1 0.1 NaOH0.2 0.2 Perfume 0.4 0.4 0.4 Polysaccharide (Xanthan Gum Kelzan 0.3 0.350.35 T ®, Kelco) Abrasive particles made from polyurethane 2 2 2 foamhaving Mean Area-equivalent Diameter (ECD): 162 μm; Mean Circularity:0.22; Mean Solidity: 0.56; Mean Roughness: 0.21 Water Balance BalanceBalance

Hand-dishwashing detergent compositions: % Weight 7 8 9 N-2-ethylhexylsulfocuccinamate 3 3 3 C11EO5 7 14 C11-EO7 7 C10-EO7 7 7 TrisodiumCitrate 1 1 1 Potassium Carbonate 0.2 0.2 0.2 Perfume 1 1 1Polysaccharide (Xanthan Gum Kelzan 0.35 0.35 0.35 T ®, Kelco) Abrasiveparticles made from polyurethane 2 2 2 foam having Mean Area-equivalentDiameter (ECD): 216 μm; Mean Circularity: 0.23; Mean Solidity: 0.66;Mean Roughness: 0.19 Water (+minor e.g.; pH adjusted to 10.5) BalanceBalance Balance

General degreaser composition: % Weight 10 11 C9-C11 EO8 (Neodol 91-8 ®)3 3 N-Butoxy Propoxy Propanol 15 15 Ethanol 10 5 Isopropanol 10Polysaccharide (Xanthan Gum-glyoxal 0.35 0.35 modified Optixan-T)Abrasive particles made from 1 1 polyurethane foam having MeanArea-equivalent Diameter (ECD): 280 μm; Mean Circularity: 0.33; MeanSolidity: 0.77; Mean Roughness: 0.15 Water (+minor e.g.; pH adjusted toBalance Balance alkaline pH)

Scouring composition: % Weight 12 13 14 Sodium C13-16 prafin sulfonate2.5 2.5 2.5 C12-14-EO7 (Lutensol AO7 ®) 0.5 0.5 0.5 Coconut Fatty Acid0.3 0.3 0.3 Sodium Citrate 3.3 3.3 3.3 Sodium Carbonate 3 3 3 Orangeterpenes 2.1 2.1 2.1 Benzyl Alcohol 1.5 1.5 Polyacrylic acid 1.5 Mw 0.750.75 0.75 Diatomaceous earth (Celite 499 ® 25 median size 10 μm) CalciumCarbonate (Merk 2066 ® 25 median size 10 μm) Abrasive particles madefrom polyurethane 5 5 5 foam having Mean Area-equivalent Diameter (ECD):216 μm; Mean Circularity: 0.23; Mean Solidity: 0.66; Mean Roughness:0.19 Water Balance Balance Balance

Liquid glass cleaner: % Weight 15 16 Butoxypropanol 2 4 Ethanol 3 6C12-14 sodium sulphate 0.24 NaOH/Citric acid To pH 10 Citric AcidAbrasive particles made from 0.5 0.5 polyurethane foam having MeanArea-equivalent Diameter (ECD): 107 μm; Mean Circularity: 0.34; MeanSolidity: 0.69; Mean Roughness: 0.12 Water (+minor) Balance Balance

Cleaning wipe (Body cleansing wipe): % Weight 17 18 19 C10 Amine Oxide —0.02 — C12,14 Amine Oxide 0.4 — — Betaine (Rewoteric AM CAS — — 0.2 15U) C9,11 A5EO (Neodol E 91.5 ®) — 0.1 — C9,11 A8EO (Neodol E 91.8 ®) — —0.8 C12,14 A5EO 0.125 — — 2-Ethyl Hexyl Sulphate — 0.05 0.6 Silicone0.001 0.003 0.003 EtOH 9.4 8.0 9.5 Propylene Glycol Butyl Ether 0.55 1.2— Geraniol — — 0.1 Citric acid 1.5 — — Lactic acid — 1.5 Perfume 0.250.15 0.15 Abrasive particles made from 0.5 gram/m² 1 gram/m² 3 gram/m²polyurethane foam having Mean Area-equivalent Diameter (ECD): 212 μm;Mean Circularity: 0.25; Mean Solidity: 0.66; Mean Roughness: 0.19Nonwoven: Spunlace 100% (x3.5) viscose 50 gsm (lotion loading fact)Nonwoven: Airlaid walkisoft (x3.5) (70% cellulose, 12% Viscose, 18%binder) 80 gsm (lotion loading factor) Carded thermobonded (70% (x3.5)polypropylene, 30% rayon), 70 gsm (Lotion loading factor) % Weight 20Benzalkonioum Chloride (Alkaquat DMB-451 ®) 0.1 Cocamine Oxide (C10/C16alkyl dimethyl amine oxide; 0.5 AO-1214 LP supplied by Procter & Gamble.Co.) Pyroglutamic Acid (pidolidone) (2-pyrrolidone-5 4 carboxylic acid)Ethanol-denatured 200 proof (SD alcohol 40 ®) 10 DC Antiform H-10(dimethicone) 0.03 Sodium Benzoate 0.2 Tetrasodium EDTA (Hampene 220 ®)0.1 Sodium Chloride 0.4 Perfume 0.01 Abrasive particles made frompolyurethane foam having Mean 2 Area-equivalent Diameter (ECD): 212 μm;Mean Circularity: 0.25; Mean Solidity: 0.66; Mean Roughness: 0.19 areloaded on the wipe e.g.: via the wipe lotion in way to achieve 0.2-3gram particles/m² substrate Water and minors balance

The above wipes lotion composition is loaded onto a water-insolublesubstrate, being a patterned hydroentangled non-woven substrate having abasis weight of 56 grams per square meter comprising 70% polyester and30% rayon approximately 6.5 inches wide by 7.5 inches long with acaliper of about 0.80 mm. Optionally, the substrate can be pre-coatedwith dimethicone (Dow Corning 200 Fluid 5cst) using conventionalsubstrate coating techniques. Lotion to wipe weight ratio of about 2:1using conventional substrate coating techniques.

Oral care composition (toothpaste): % Weight 20 21 Sorbitol (70% sol.)24.2 24.2 Glycerin 7 7 Carboxymethylcellulose 0.5 0.5 PEG-6 4 4 SodiumFluoride 0.24 0.24 Sodium Saccharine 0.13 0.13 Mono Sodium phosphate0.41 0.41 Tri Sodium phosphate 0.39 0.39 Sodium Tartrate 1 1 TiO2 0.50.5 Silica 35 Sodium lauroyl sarcosinate (95% active) 1 1 Flavor 0.8 0.8Abrasive particles made from 2 5 polyurethane foam having MeanArea-equivalent Diameter (ECD): 107 μm; Mean Circularity: 0.34; MeanSolidity: 0.69; Mean Roughness: 0.12 Water Balance Balance

Body Cleansing composition: % Weight 22 23 Cocoamidopropyl betaine 5.155.15 Sodium Laureth sulfate 5.8 5.8 Sodium Lauroyl sarcosinate 0.5 0.5Polyquaternium 10 0.1 0.1 C12-14 fatty alcohol 0.45 0.45 Zinc Stearate1.5 1.5 Glycol DiStearate 0.25 0.25 Sodium lauryl sulfate 0.53 0.53Cocamidopropyl betaine 0.17 0.17 Lauramide Diethanolamide 0.48 0.48Sodium sulfate 0.05 0.05 Citric Acid 0.05 0.05 DMDM hydantoin(1,3-Dimethylol-5,5- 0.2 0.2 dimethylhydantoin Glydant) Tetra SodiumEDTA 0.1 0.1 Fragance 0.5 0.5 Polysaccharide (Xanthan Gum-glyoxal 0.20.2 modified Optixan-T) Abrasive particles made from 2 1 polyurethanefoam having Mean Area-equivalent Diameter (ECD): 216 μm; MeanCircularity: 0.23; Mean Solidity: 0.66; Mean Roughness: 0.19 Water andminors 1 Water Balance Balance

Facial Cleansing Compositions Ingredients 24 25 26 27 AcrylatesCopolymer¹ 1.50 2.0 1.25 — Acrylates/C₁₀₋₃₀ alkyl acrylate — — — 1.0crosspolymer² Sodium Lauryl Sulfate 2.0 — — — Sodium Laureth Sulfate 8.0— — — Ammonium Lauryl Sulfate — 6.0 — — Sodium Trideceth Sulfate — — 3.02.5 Sodium Myristoyl Sarcosinate — 2.0 3.0 2.5 Sodium Lauroamphoacetate³— — 6.0 5.0 Sodium Hydroxide* pH >6 — — — Triethanolamine* — pH >6 — pH5.2 Cocamidopropyl Betaine 4.0 7.0 — — Glycerin 4.0 5.0 2.0 2.0 Sorbitol— — 2.0 2.0 Salicylic Acid — — 2.0 2.0 Fragrance 0.1 0.1 0.1 0.1Preservative 0.3 0.3 0.15 0.15 Abrasive particles made from 1.0 1.0 2.02.0 polyurethane foam having Mean Area-equivalent Diameter (ECD): 216μm; Mean Circularity: 0.23; Mean Solidity: 0.66; Mean Roughness: 0.19PEG 120 Methyl Glucose 0.5 — 0.25 0.25 Trioleate⁴ PEG 150Pentaerythrityl — 0.40 — — Tetrastearate⁵ Citric Acid** pH 5.5 pH 5.5 pH5.5 pH 5.5 Water QS to 100% QS to 100% QS to 100% QS to 100% *per thesupplier use directions, the base is used to activate the acrylatescopolymer **acid can be added to adjust the formula to a lower pH¹Carbopol Aqua SF-1 ® from Noveon ™, Inc. ²Carbopol Ultrez 21 ® fromNoveon ™, Inc. ³Miranol ® Ultra L32 from Rhodia ⁴Glucamate LT ® fromChemron ⁵Crothix ® from Croda

Examples 24 to 27 are made the following way:

Add Carbopol® to de-ionized free water of the formulation. Add allsurfactants except cationics and betaines. If the pH is less than 6 thenadd a neutralizing agent (typically a base i.e., Triethanolamine, sodiumhydroxide) to adjust to a pH greater than 6. If necessary, apply gentleheat to reduce viscosity and help minimize air entrapment. Add betaineand/or cationic surfactants. Add conditioning agents, additionalrheology modifiers, pearlizing agents, encapsulated materials,exfoliants, preservatives, dyes, fragrances, abrasive particles andother desirable ingredients. Lastly, if desired reduce the pH with anacid (i.e. citric acid) and increase viscosity by adding sodiumchloride.

Oral care composition (toothpaste) 28 29 30 31 32 Sodium Gluconate 1.0641.064 1.064 1.064 0.600 Stannous fluoride 0.454 0.454 0.454 0.454 0.454Sodium fluoride Sodium monofluorophosphate Zinc Lactate 0.670 0.6700.670 0.670 2.500 Glycerin — — — — 36.000  Polyethylene glycol 300 7.000Propylene Glycol 7.000 Sorbitol(LRS) USP 39.612  39.612  39.612  39.612 — Sodium lauryl sulfate 5.000 5.000 5.000 5.000 3.500 solution (28%)Abrasive particles 10.000  10.000  1.000 5.000 5.000 made frompolyurethane foam having Mean Area-equivalent Diameter (ECD): 216 μm;Mean Circularity: 0.23; Mean Solidity: 0.66; Mean Roughness: 0.19Zeodent 119 — — — — — Zeodent 109 10.000  10.000  10.000  Hydrogenperoxide (35% soln) Sodium — — — — 13.000  hexametaphosphate Gantrez2.000 2.000 2.000 — Natural CaCO3-600M — — — — — Sodium phosphate — — —— — (mono basic) Sodium phosphate — — — — 1.000 (Tri basic) Zeodent 165— — — — — Cocoamidopropyl — — — — — Betaine (30% Soln) Cetyl Alcohol3.000 — — — — Stearyl Alcohol 3.000 — — — — Hydroxyethyl cellulose —0.500 0.500 0.500 — (HEC Natrasol 250M) CMC 7M8SF — 1.300 1.300 1.300 —Xanthan Gum — — — — 0.250 Poloxamer 407 — — — — — Carrageenan mixture —0.700 0.700 0.700 0.600 Titanium dioxide — — — — — Saccharin Sodium0.500 0.500 0.500 0.500 0.500 Flavor 1.000 1.000 1.000 1.000 1.000 WaterQS QS QS QS QS

Zeodent 119, 109 and 165 are precipitated silica materials sold by theJ. M. Huber Corporation.

Gantrez is a copolymer of maleic anhydride or acid and methyl vinylether.

CMC 7M8SF is a sodium carboxymethylcellulose.

Poloxamer is a difunctional block-polymer terminating in primaryhydroxyl groups.

33 34 35 36 37 Sodium Gluconate — — — — — Stannous fluoride — — — — —Sodium fluoride — 0.243 0.243 0.243 — Sodium 1.10  — monofluorophosphateZinc Lactate — — — — — Glycerin — — — — 40.000  Polyethylene glycol 300— — — — — Propylene Glycol Sorbitol(LRS) USP 24.000  42.500  42.500 42.500  30.000  Sodium lauryl sulfate 4.000 4.000 — 4.000 — solution(28%) Abrasive particles made 5.000 10.000 10.000  5.000 15.000 frompolyurethane foam having Mean Area- equivalent Diameter (ECD): 216 μm;Mean Circularity: 0.23; Mean Solidity: 0.66; Mean Roughness: 0.19Zeodent 119 — — — 10.000  — Zeodent 109 Hydrogen peroxide (35% soln)Sodium — — — — — hexametaphosphate Gantrez Natural CaCO3-600M 35.00  — —— — Sodium phosphate 0.10  0.420 0.420 0.420 0.420 (mono basic) Sodiumphosphate 0.40  1.100 1.100 1.100 1.100 (Tri basic) Zeodent 165 2.00 — —— 2.000 Cocoamidopropyl — — 5.000 — — Betaine (30% Soln) Cetyl Alcohol0.000 — — — — Stearyl Alcohol 0.000 — — — — Hydroxyethyl cellulose —0.500 0.500 0.500 — (HEC Natrasol 250M) CMC 7M8SF 1.300 1.300 1.3001.300 1.300 Xanthan Gum — — — — — Poloxamer 407 — — — — — Carrageenanmixture — 0.700 0.700 0.700 — Titanium dioxide — — — — — SaccharinSodium 0.250 0.500 0.500 0.500 0.500 Flavor 1.000 1.000 1.000 1.0001.000 Water QS QS QS QS QS 38 39 40 Sodium Gluconate — — 1.500 Stannousfluoride — — 0.454 Sodium fluoride — — — Sodium monofluorophosphate — —— Zinc Lactate — — — Glycerin 40.000  10.000  25.000  Polyethyleneglycol 300 3.000 — — Propylene Glycol — — — Sorbitol(LRS) USP — 39.612 — Sodium lauryl sulfate solution (28%) 5.000 4.000 4.000 Abrasiveparticles made from 15.000  5.000 5.000 polyurethane foam having MeanArea- equivalent Diameter (ECD): 216 μm; Mean Circularity: 0.23; MeanSolidity: 0.66; Mean Roughness: 0.19 Zeodent 119 — — — Zeodent 109Hydrogen peroxide (35% soln) — 8.570 8.570 Sodium hexametaphosphate14.000  — — Gantrez — — — Natural CaCO3-600M — — — Sodium phosphate(mono basic) 0.420 — — Sodium phosphate (Tri basic) 1.100 — — Zeodent165 2.000 — — Cocoamidopropyl Betaine (30% Soln) — — — Cetyl Alcohol —3.000 — Stearyl Alcohol — 3.000 — Hydroxyethyl cellulose (HEC Natrasol —— — 250M) CMC 7M8SF 1.000 — — Xanthan Gum 0.300 — — Poloxamer 407 0.500— 18.000  Carrageenan mixture — — — Titanium dioxide 0.500 — — SaccharinSodium 0.500 0.500 0.500 Flavor 1.000 1.000 1.000 Water QS QS QS

Hair Shampoo 41 42 43 Water q.s. q.s. q.s. Polyquaterium 76¹ 0.25 — —Guar, Hydroxylpropyl Trimonium — 0.25 — Chloride² Polyquaterium 6³ — —0.25 Sodium Laureth Sulfate 12 10.5 10.5 Sodium Lauryl Sulfate 1.5 1.5Silicone⁴ 0.75 1.00 0.5 Cocoamidopropyl Betaine 3.33 3.33 3.33 CocoamideMEA 1.0 1.0 1.0 Ethylene Glycol Distearate 1.50 1.50 1.50 Abrasiveparticles made from 1 2 polyurethane foam having Mean Area-equivalentDiameter (ECD): 216 μm; Mean Circularity: 0.23; Mean Solidity: 0.66;Mean Roughness: 0.19 Crosslinked PS-DVB (50% DVB 55, 1 mean diameterD(v, 0.9) 75 μm) abrasive cleaning particles Fragrance 0.70 0.70 0.70Preservatives, pH & Visc. adjusters Up to 1% Up to 1% Up to 1%¹Copolymer of Acrylamide(AM) and TRIQUAT, MW = 1,000,000; CD = 1.6meq./gram; Rhodia ²Jaguar C500, MW - 500,000, CD = 0.7, Rhodia ³Mirapol100S, 31.5% active, Rhodia ⁴Dimethicone Fluid, Viscasil 330M; 30 micronparticle size; Momentive Silicones

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application, is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests ordiscloses any such invention. Further, to the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

1. A liquid cleaning and/or cleansing composition comprising abrasivecleaning particles, wherein said abrasive cleaning particles have meancircularity from about 0.1 to about 0.4 and wherein abrasive cleaningparticles have VH Vickers hardness from 3 to 50 kg/mm².
 2. A liquidcleaning and/or cleansing composition according to claim 1, wherein saidabrasive cleaning particles have mean circularity from about 0.15 toabout 0.35, wherein the circularity is measured according to ISO 9276-6.3. A liquid cleaning and/or cleansing composition according to claim 1,wherein said abrasive particles have HV Vickers hardness from about 4 toabout 25 kg/mm², wherein said HV Vickers hardness is measured accordingto method disclosed herein.
 4. A liquid cleaning and/or cleansingcomposition according to claim 3, wherein said abrasive particles have amean particle size as expressed by the area-equivalent diameter fromabout 10 to about 1000 μm, according to ISO 9276-6
 5. A liquid cleaningand/or cleansing composition according to claim 4, wherein saidcomposition comprises abrasive particles from about 0.1%, to about 20%by weight of the composition.
 6. A liquid cleaning and/or cleansingcomposition according to claim 5, wherein said abrasive cleaningparticles have mean roughness from about 0.1 to about 0.3, wherein meanroughness is measured according to method disclosed herein.
 7. A liquidcleaning and/or cleansing composition according to claim 6, wherein saidabrasive cleaning particles have mean solidity from about 0.4 to about0.75, wherein mean solidity is measured according to ISO 9276-6.
 8. Aliquid cleaning and/or cleansing composition according to claim 7,further comprises a suspending aid, wherein said suspending aid isselected from the group consisting of polycarboxylate polymerthickeners; hydroxyl-containing fatty acid, fatty ester or fatty soapwax-like materials; carboxymethylcellulose, ethyl cellulose,hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxymethylcellulose, succinoglycan and naturally occurring polysaccharide polymerslike Xanthan gum, gellan gum, guar gum, locust bean gum, tragacanth gum,succinoglucan gum, or derivatives thereof, or mixtures thereof.
 9. Aliquid cleaning and/or cleansing composition according to claim 8,wherein said abrasive cleaning particles are reduced into particles frompolymeric material by grinding or milling, and wherein polymericmaterial is selected from the group consisting of polyethylene,polypropylene, PVC, polycarbonate, melamine, urea, polyurethane,polyacrylate, polystyrene, phenolic, polyesters, polyamide and mixturesthereof.
 10. A liquid cleaning and/or cleansing composition according toclaim 9, wherein said abrasive cleaning particles are reduced intoparticles from foamed polymeric material by grinding or milling andwherein foamed polymeric material is selected from the group consistingof polyethylene, polypropylene, PVC, polycarbonate, melamine, urea,polyurethane, polyacrylate, polystyrene, phenolic, polyesters, polyamideand mixtures thereof.
 11. A liquid cleaning and/or cleansing compositionaccording to claim 10, whereas the cleaning composition is loaded on acleaning substrate whereas the substrate is a paper or nonvowen towel orwipe or a sponge.
 12. A process of cleaning and/or cleansing a surfacewith a liquid, cleaning and/or cleansing composition according to claim10, wherein said surface is contacted with said composition, and whereinsaid composition is applied onto said surface.
 13. A process accordingto claim 12, wherein said surface is an inanimate surface, selected fromthe group consisting of household hard surfaces; dish surfaces; surfaceslike leather or synthetic leather; and automotive vehicle surfaces. 14.A process according to claim 12, wherein said surface is an animatesurface, selected from the group consisting of: human skin; animal skin;human hair; animal hair; and hard and soft tissue surface of the oralcavity, such as teeth, gums, tongue and buccal surfaces.